Nanomaterials 2013, 3, 325-356; doi:10.

3390/nano3030325

nanomaterials
ISSN 2079-4991
www.mdpi.com/journal/nanomaterials
Review
Photoelectrochemical Properties of Graphene and
Its Derivatives
Alberto Adán-Más
1
and Di Wei
2,
*
1
Department of Materials Science and Metallurgy, University of Cambridge, CB2 3QZ, UK;
E-Mail: aa744@cam.ac.uk
2
Nokia Research Centre, Broers Building, 21 JJ Thomson Ave., Cambridge CB3 0FA, UK
* Author to whom correspondence should be addressed; E-Mail: di.wei@nokia.com;
Tel.: +44-782-687-1586.
Received: 14 May 2013; in revised form: 20 June 2013 / Accepted: 20 June 2013 /
Published: 3 July 2013

Abstract: Graphene and its derivatives combine a numerous range of supreme properties
that can be useful in many applications. The purpose of this review is to analyse the
photoelectrochemical properties of pristine graphene, graphene oxide (GO) and reduced
graphene oxide (rGO) and their impact on semiconductor catalysts/quantum dots. The
mechanism that this group of materials follows to improve their performance will be
cleared by explaining how those properties can be exploited in several applications such as
photo-catalysts (degradation of pollutants) and photovoltaics (solar cells).
Keywords: graphene oxide; graphene; reduced graphene oxide; photocatalysis;
photoelectrochemistry

1. Introduction
Global warming and the increment of pollutant concentrations are just two of the environmental
issues associated with societal development. One possible way to address those and other existing
environmental problems could be through the development of highly-efficient photocatalysts;
exploiting processes that are based in solar energy. Semiconductor-based photocatalysis relies on the
active absorption of a photon from a semiconductor to create an electron-hole pair. This process
depends on the band gap of the material [1]. Then, the excited electron has to be separated from the
hole created to avoid recombination. This can be used to generate an ultrafast photocurrent
OPEN ACCESS
Nanomaterials 2013, 3 326


response [2]. The electron can also be used to reduce chemicals in the environment by generating
radical species such as hydroxyl radicals; which can initiate, for example, degradation reactions [3].
For a semiconductor to be considered a good photocatalyst, the compound must be photoactive, it
must have different electron and hole processes so they do not recombine, it must be able to absorb UV
and visible radiation effectively, be photo-stable and be biologically and chemically inert, with the
exception of the reaction that it has to catalyze. Besides, in order to be mass-produced, it has to be easy
to fabricate, cost effective and non-toxic. Some of the most adequate and traditionally studied
semiconductors are TiO
2
, ZnO, CdS, ZnS and Fe
2
O
3
[1,3]. Nevertheless, those materials have some
limitations (e.g., TiO
2
has a limited photoactivity with the radiation provided by solar light [4]) that
can be potentially overcome by the use of graphene and its derivatives.
Within the reviewed literature, some authors refer to reduced graphene oxide (rGO) as graphene
(G); however, they have different physicochemical properties, which may affect the obtained results.
Therefore, they are differentiated throughout the content of this work.
2. Graphene Properties
Graphene, a single layer or few layers of graphite with sp
2
carbon atoms packed in a honeycomb
crystal lattice [5], has unique properties that have been researched for the last decade, since it was first
isolated in 2004 [6,7]. In order to exploit these properties, potential applications are being developed.
An example of that is photo-detectors and plasmonic devices, which are based on its electrical and
optical properties [8,9]. The material has different interesting properties such as large surface area
(2630 m
2
g
−1
) [10], gas impermeability, very high thermal conductivity (>3000 W mK
−1
), and
extremely high Young’s Modulus (1 TPa), amongst others [11].
Electrical and optical properties are two of the most novel convenient advances for photocatalysis.
Since the electronic structure of a single layer of graphene (SLG) overlap between two conical points
in the Brillouin zone, the charge carriers can be understood as mass-less electrons or Dirac
fermions [5,12]. Graphene monolayers have an electrical conductivity of (4.84–5.30) 103 W mK
−1
and
charge mobility of ≈200,000 cm
2
V s
−1
. Besides, charge density can be controlled with a gate electrode
and it has ballistic transport (negligible electrical resistivity) [5,13]. It is ambipolar (“charge carriers
can be alternated between holes and electrons depending upon the nature of the gate voltage”) and,
finally, has anomalous quantum hall effect [5,14]. Regarding the optical properties of graphene, it
almost has total transparency. A SLG can absorb a 2.3% fraction of light with a very wide spectral
width. Besides, its high operating bandwidth allows to process data at high velocities [2,11]. Moreover,
the absorption range can be modified in double-layer graphene by tuning the electrical gating.
Therefore, by means of an external gate field, the Fermi energy levels of graphene are changed
modifying the absorption properties [2,15].
Finally, chemical properties and chemical modification is also of particular interest in photocatalysis
since it enables the adjustment of several of graphene’s properties. The objectives behind functionalization
are multiple. For example, the problems encountered by the absence of a gap in graphene (and the
consequent absence of photoluminescence) can be solved by widening the band-gap through the coupling
between graphene and a substrate. Furthermore, the presence of oxides can vary the properties of graphene,
influencing the adsorption and desorption of molecules and, therefore, the chemical reactions. This can
Nanomaterials 2013, 3 327


lead to an improvement of the catalytic properties of graphene by functionalization [12,13]. The
reactivity of graphene is not fully understood yet but in order to generate covalent bonds from pristine
graphene, it requires the breaking of a sp
2
bond. In the adjacent regions to that break point, reactivity is
enhanced, as well as the geometrically strained regions [14]. However, it is remarkable that rGO and
graphene oxide (GO) have oxygen groups that act as reactive regions.
3. Graphene Oxide Properties
The main derivative of graphene is graphene oxide (GO), which can be directly synthesized from
graphite oxide. In this review, we will consider graphene, rGO and graphene oxide-based semiconductor
photocatalysers. GO, represented in Figure 1, contains functional oxygen groups (hydroxyl, epoxy,
carbonyl and carboxyl) in sp
3
carbons that vary the properties from pristine graphene [14,15]. Those
components are usually the starting point of chemical reactions towards functionalization of graphene.
Although the chemistry is still under debate, these oxygen-containing groups provide graphene with
hydrophilic character and chemical reactivity [15].
Figure 1. Graphene oxide structure representation. Reprinted with copyright permission
from reference [15]. Copyright © 2012, American Chemical Society.

GO also has some other interesting properties. It is an amphiphile with hydrophilic edges that can
act as surfactant [16], it is water permeable and ferromagnetic (which is believed to be produced by the
defects on graphene structure) [17,18]. Monolayer GO has a lower Young Modulus value than pristine
graphene with a value of approximately 207 GPa and a pre-stress oscillating between 39.7 and
76.8 MPa when an average thickness of 0.7 nm of the sample is tested [19]. Moreover, it is an
insulating material (the C–O bonds break the conjugation in the lattice, lateral resistivity values of
10
5
Ω·cm
−1
[20]) but, by means of a controlled process of deoxidation, an optically and electrically
active material can be produced, turning it into a transparent and conductive sample [21]. The vertical
resistivity of GO is an order of magnitude lower than the lateral resistivity

[20]. These low values of
electrical conductivity are maintained in aqueous solutions, where it shows a value of 17 S/m, a very
small value compared to reduced graphene oxide in the same conditions (1250 S/m). This proves a
restoration of the conjugated system [22].
Nanomaterials 2013, 3 328


One interesting property in photocatalyser materials is photoluminescence. In GO, instead of having
fluorescence from band-edge transitions (this is the case in semiconductors), the exciton recombination
is localized in electronic states with various possible configurations [21]. The advantages of this effect
are faster electron transport, lower recombination and higher light scattering; which increase the
overall efficiency of the catalyser [20].
Regarding the photoelectrochemical current response achieved with GO, Zhang et al. showed that
the cathodic photocurrent can be increased by increasing the film thickness, and decreased by UV
irradiation. For an average of 9 nm in film thickness, 0.10 µA·cm
2
of photocurrent density was
achieved. It increases to 0.25 µA·cm
2
for a thickness of 27 nm. Therefore, by controlling the thickness
of the film and the time of exposure under UV light, the photoelectrochemical properties of GO can be
tuned [23].
A possible explanation is that GO acts as a p-type semiconductor; thus, when it is under
illumination the holes tend to go into the GO layer while the electrons are driven to the surface,
generating the cathodic photocurrent. Those electrons are captured by the water particles that have
been adsorbed on the electrode surface and, after the reaction, they produce hydrogen. The effect
produced by UV is related to the behaviour of the oxygen groups and their variation in content. It is
also remarkable that the optical band gap of GO is around 3.06 eV and the film thickness nearly has no
effect on the optical band of GO [23].The maximum value of capacitance in rGO obtained is 205 F/g
with a power density of 10 kW/kg in an aqueous electrolyte with an energy density of 28.5 Wh/kg.
Usually, high surface materials in the effective surface area depends on the distribution of pores at
solid state. However, this is not the case for reduced graphene oxide. It depends on the number of
layers—the fewer number of layer, the less agglomeration and, therefore the best capacitance
results [24].
Yang et al. coated chalcogenide T4 clusters with rGO to avoid the decomposition of the clusters.
This coat not only enabled photo-induced charge separation but also improved by 141% the
photoconversion rate of the cluster. Since rGO does not have an energy gap, they are supposed to trap
temporary the photo-generated electrons with the consequent reduction of surface recombination. In a
Nyquist plot the smaller the radius, the better the charge transfer ability. When rGO was applied the
radius was smaller, proving that the separation was more effective and the interfacial charge transfer
occurred at the interface of the cluster with rGO. The electrons that are generated in the cluster were
captured by rGO and then transferred, avoiding the direct recombination. Besides, it prevented the
photo-corrosion. Similar results were found with GO; however, since it is much less conductive, the
rate of photocurrent achieved was smaller [25].
Bell et al. characterized the photoelectrochemical properties of rGO by using a three-compartment cell
comparing the results between rGO/TiO
2
/FTO and TiO
2
/FTO composites. The magnitude of the
anodic photocurrent generated by illuminating the film was determined by two factors. First, the speeds at
which electrons withdraw from TiO
2
to FTO. Second, the current lost as a result of recombination
within the film and at the film/electrode interface, rGO improved the photocurrent of the system in a
factor of 1.5–3 times. Moreover, the transient photocurrent decay (that provides qualitative
understanding of the charge recombination behaviour) is increased from 3 to 6 s. This effect reveals
that the presence of rGO increases dramatically the lifetime of the electron within the film [26].
Nanomaterials 2013, 3 329


By studying the conductance and capacitance of the same system, they determined an optimal ratio
for TiO
2
:rGO of 0.7:4 mg, which shows that the conductivity can be prejudiced by light-blocking
through rGO. It also facilitates the conduction between the nanoparticles film and the substrate which
may be useful to construct a photovoltaic cell that exhibits 10 times more photocurrent [26]. This level
of increase is not always achieved; however, there is always a significant enhancement of the photocurrent
due to the activity of rGO, for example, from approximately 20 µA/cm
2
to 38 µA/cm
2
under UV light
in a photoelectrochemical cell. If the photocurrent calculated is normalized, the maximum increment in
value provided by rGO in the same system was a 6.5% for Yun et al. [27].
Unlike graphene that is hydrophobic, both GO and rGO can be stabilised in water to form stable
colloids by means of electrostatic stabilization, without the need of foreign stabilizers. Through zeta
potential experiments, the stability of these dispersions has been studied. It is pH dependent and lower
than −30 mV at pH greater than 6.1. When the zeta potential reaches a value of −30 mV, it is considered
that there is enough repulsion to prove the stability of dispersion. The electrical conductivity achieved
for water-dispersed rGO goes up to 7200 S·m
−1
. The tensile modulus is 35 GPa, it is flexible and
thermally stable. The resistivity is 2.0·× 10
7
Ω·m at RT with a transmittance of 96% [28].
It is remarkable that, at the moment, only rGO and not pure graphene flakes can be found in
aqueous solution. Therefore, the electrochemical properties are always related to this derivative. The
electrochemical potential for reduced graphene oxide is 2.5V in 0.1 M PBS (pH 7.0) while the charge
transfer resistance determined from AC impedance is much lower than in graphite and glassy carbon
electrodes. The electron transfer behavior and the consequent redox peaks are studied in cyclic
voltammetry, which show very well-defined peaks. Besides, the fact that the anodic and cathodic peak
currents are linear with the square root of the scan rate indicates that, probably, these redox processes
are controlled by diffusion. The ideal peak-to-peak potential is set to be 59 mV. In the case of rGO’s
CV, the value is extremely close. This value is related to the electron transfer coefficient, indicating a
very high single-electron electrochemical reaction. The value for the electron transfer constant in the
edge plane is 0.18 cm/s, much higher than 0.055 cm/s obtained for glassy carbon electrodes in a
system with [Ru(NH
3
)
6
]
3+/2+
as a redox couple. This experience has been tested with other redox
couples and it has always indicated that the electronic structure and the surface physicochemistry are
extremely enhanced in electron transfer processes on rGO. In the basal plane it is inert electrochemically,
with a transfer constant below 10
−9
cm/s [29]. The electrochemistry of rGO is controlled by its edges.
In them, the heterogeneous electron transfer (HET) is fast, which determines the good redox peaks
obtained in the electrochemical tests [30].
If rGO is used in cyclic voltammograms as an electrode in 1.0 M LiPF
6
with Li as counter and
reference electrode, the cathodic current generated is similar to graphite with large initial current loss
and no anodic current. Nevertheless, in the second cycle it loses all charge capacity retaining only a
12.4% of its original capability. However, the first discharge had a discharge capacity of 528 mA·h·g
−1

with a cutoff voltage of 2.0 V. The specific energy density was 1163 W·h·kg
−1
. These values show
the really promising electrochemical possibilities of this material, which are quite different from
graphite [31].
To summarize, graphene and graphene oxide have an extensive surface area, being an excellent
substrate for semiconductor particles, excellent mechanical and optical properties. The optoelectronic
and chemical properties are the main difference between the two materials. Graphene has excellent
Nanomaterials 2013, 3 330


conductivity and transparency while GO is a more opaque insulator. However, GO can be either
chemically functionalized or reduced to produce rGO. With these materials, a tuneable band gap can
be achieved with low recombination rate and high photocurrent response.
4. Production
Before dealing with the production of graphene/semiconductor photocatalysts, it is important to
understand the different production methods of graphene and its derivatives. They are the key to
generating graphene, rGO or GO and therefore, different properties. The first demonstration of
isolation was done by Novoselov et al. with the “Scotch tape method”, where bulk graphite was placed
on the sticky side of regular tape and peeled away. Since that moment, many synthesis procedures to
obtain graphene have been developed [7,32,33]. Many groups have already compiled different
production methods, such as the work done by Cooper et al. and the articles published by Zhu et al.
and Kuila et al. [34–36].
One example of graphene synthesis is the photolithographically patterned trenches developed by
Frank et al. that shear off graphite which is then rubbed on silicon dioxide to produce graphene [37].
Some other examples are molecular beam epitaxial growth on SiC by thermal decomposition [38,39];
solvothermal synthesis (a pyrolysis of an alcohol, usually nano-dispersed ethanol, and an alkali metal
(Na) that gives fused monoatomic sheets of graphene) [40]; unzip of multi-walled carbon nanotubes
(MWCNTs can be cut longitudinally if they are first suspended in H
2
SO
4
/KMnO
4
); electron beam
irradiation of Poly(methyl methacrylate) (PMMA) nanofibres, arch discharge of graphite, thermal
fusion of PAHs and conversion of nanodiamond [35].
Large area films of graphene are produced by chemical vapour deposition (CVD) based on the
reaction of carbon-based gases on a metal catalyst [32,33]. A metal substrate is placed into a furnace
and heated at low vacuum at high temperatures to increase its domain size by annelation. Then,
methane and hydrogen gases are inserted into the furnace. Carbon atoms are deposited on the surface
of the substrate through chemical adsorption with hydrogen as a catalyst. When the furnace is
cooled, it crystallizes into single layer graphene (SLG) [33]. This technique has been developed on top
of various metal substrates (Pt, Ni, Fe, Pd and Co). It has also been modified to generate other
enhanced synthesis techniques, namely remote plasma-enhanced CVD, surface wave plasma,
inductively-coupled-plasma CVD and roll-to-roll production [41,42]. One of the advantages of this
technique is the ease to transfer the SLG to other substrates by means of polymer substrates [43].
From the aforementioned techniques, only graphene grown by CVD on different metals and their
modifications are, currently, scalable processes. Roll-to-roll technique is a promising technique that
can allow sample transfers, produce good quality graphene and can be scaled-up [42,43]. However,
since pristine graphene has no functional groups, it makes infeasible dispersion and contact with
photocatalysts [10].
Other relevant production methods are based on the obtainment of reduced Graphene Oxide. Thus,
GO production methods shall be addressed first. The most important methods of GO synthesis
are mainly based on three graphite oxidation procedures. In the first one, KClO
3
reacts with graphite
in fuming HNO
3
. The second method is a modification replacing KClO
3
with H
2
SO
4
. In the third
place, a process generally known as Hummers method, a mixture of KMnO
4
and H
2
SO
4
reacts with
Nanomaterials 2013, 3 331


graphite to form oxide graphite. These three methods of wet chemical synthesis are the basis of GO
production [44].
Probably, the most commonly used techniques are variations of Hummer’s method. Raw graphite is
oxidized using KMnO
4
:H
2
SO
4
and NaNO
3
producing positively charged carbon layers with negative
hydrogen-sulphate ions. The two layers increase their distance by hydrolyzing the compounds between
the carbon layers. Then, by removing the extra ions produced by the oxidants, the layers tend to
separate automatically and thin-film particles in aqueous solution are obtained. After several
treatments, uniform-thin graphene oxide films are produced [45–47].
Moreover, there are other methods of producing GO; namely, sonication of graphite oxide and
RF Plasma functionalization (produces GO by etching the graphite surface and selectively oxidize
SLG and the top later of multilayer samples. It is used for photoluminescence and optoelectronic
purposes) [35,48,49].
As far as the scalability of GO production techniques is concerned, they have been proved to be
efficient in graphene-based semiconductors production. By concrete conditions of the Hummer’s
method, (no Na
3
NO
3
, increased amount of KMnO
4
and H
2
SO
4
:H
3
PO
4
in a 9:1 mixture) fewer defects,
higher yield, equivalent conductivity and no production of toxic gases is achieved. Therefore, this is
considered to be the most suitable method to prepare graphene oxide in large quantities [10,50].
Once GO is produced, reduced graphene oxide can be obtained by means of reducing agents. There
are two main reaction groups, chemical and non-chemical reductions. The former group is based on
liquid-phase exfoliation, an intermediate process between exfoliation and chemical growth where GO
obtaining methods are applied with a following chemical reduction [45–47]. The reducing agents are
varied: hydrazine hydrate [51], NaBH
4
[52], sodium hydrosulfite [53], iron/HCl [54] and other metals
like aluminium , acetic acid/HCl [55] amongst others [34].
A variation of liquid-phase exfoliation is electrochemical exfoliation, a green mass-production
technique to obtain exfoliated graphene flakes. By using a mixture of solvents with narrow
electrochemical window (e.g., water) and a liquid with large electrochemical window [e.g., room
temperature ionic liquid (RTIL)], hydroxyl and oxygen radicals can be produced by the electrolysis of
water. Then, the oxygen radicals corrode the graphite anode on defect sites, grain boundaries and edge
sites. This induces the separation of the edge sheets and the intercalation of RTIL anions within the
sheets. The electrode is expanded and provokes the precipitation, which makes the sheets precipitate,
generating a graphene solution. This is a relevant technique since it can produce rGO with reduced
sheet resistance (0.015–0.21 KOhm/sq in comparison to 1–100 KOhm/sq obtainable by chemical
reduction) and greater transparency (96% versus the 80% achievable by means of chemical reduction).
This would greatly affect the final photoelectrochemical performance of the material. The reduction
and exfoliation level and the size of rGO sheets are controlled by tuning the applied potential and
varying the RTIL [56].
Thermal treatment is a low cost method [36]. Some other methods are microwave-induced
reduction [57], flash reduction [58] and solvent-assisted thermal reduction [59], but, as in the case of
GO, many other production methods are being continuously developed. The objective is to achieve
large-scale production methods of quality graphene [34,36].
As far as the interaction between semiconductors and rGO is concerned, the remaining
oxygen-containing groups interact with the semiconductor to attach it. The problem is that Hummer’s
Nanomaterials 2013, 3 332


method produces a large number of defects. Hence, they reduce the recombination probability, so
alternative methods are being developed to reduce the quantity of defects produced. Examples of this
are solvent-exfoliated graphene and non-oxidative preparation of graphene with a mixture of water and
ethylene glycol by an ultrasonic reaction. These methods would be upscalable and are the leading edge
towards mass production of quality graphene [10].
5. Photoelectrochemical Cells
In order to understand the photoelectrochemical properties of graphene and its derivatives,
numerous examples of existing applications are reviewed in this article. However, it is important to
clarify that the main subfield considered in this review is photocatalysis, which is only a subgroup
within photoelectrochemistry. Thus, we shall also briefly consider photoelectrochemical cells, the
other main photoelectrochemical subgroup [60].
A photoelectrochemical cell is a photocurrent-generated device composed of an electrolyte, a
photoactive semiconductor electrode and a counter electrode. In the case of irradiation of the interface
electrolyte-semiconductor with an energy level greater than the band gap of the semiconductor,
electron-hole pairs are generated. The charge in a semiconductor is distributed creating a space charge
region that enables the separation of the electron-hole pairs. The minor carriers arrive at the electrolyte
while the major carriers travel to the counter electrode by means of a wire to react with the redox
couple. There is one main alternative to the traditionally used Si-based solar cells that has been notably
improved by any of graphene’s derivatives. This type of photoelectrochemical cells is dye-sensitized
solar cells; although there have been also important improvements in quantum dot solar cells which are
briefly discussed in another section of this review [60,61].
Dye-sensitized solar cells (DSSCs) will be considered again in this review in solar cell devices.
However, the contribution of graphene and derivatives has been remarkable in improving these
systems. Therefore, a brief and more general review shall be undertaken.
DSSCs are formed by three main parts. A semiconductor with a dye that is deposited on top of a
transparent conducting oxide (FTO, ITO are the most usual), a redox couple in an organic electrolyte
(I
3−
/I

) and finally, a counter electrode coated with platinum where the redox couple is restored. In this
case, the photo-induced electron-hole pair is tightly bonded together, forming an exciton with higher
energy than thermal agitation [62]. There are many challenges to overcome such as the suppression of
the charge recombination [60].
Graphene can be a substitute of the transparent electrode. A transparency of 70% in the
1000–3000 nm range with a conductivity of 550 S·cm
−1
was obtained by using rGO. However, the
performance of the device was lower than the analogous system with FTO instead [60]. Another
possibility is to use graphene as a junction material between the semiconductor particle and the
transparent oxide layer. Li et al. reported a composite rGO/TiO
2
on top of FTO, obtaining better
performance than the same device without rGO with a PCE from 5.8% to 8.13% [63].
As far as the electrolyte is concerned, the carbon materials can be simultaneously used as charge
transporter in the ionic liquid and as a catalyst for the redox couple reaction. Ahmad et al. experienced
that—when adding rGO to the PMII electrolyte, the light conversion efficiency increased from 0.16%
Nanomaterials 2013, 3 333


to 2.1%. Moreover, when a mixture of rGO and SWCNTs was introduced, the efficiency increased by
up to 2.5% [64].
Graphene is also a good candidate to replace semiconductor oxides and act as a photoanode. The
properties that a photoanode should have are highly active surface area, easy fabrication and capability
to perform fast electron transport. Since the most important semiconductor is TiO
2,
most of the work is
related to mixtures of this material with some graphene derivative. The DSSC current can be improved
obtaining higher PCE, as shown by Nair et al., where it improved from 6.3% to 7.6%. The top value of
PCE achieved for this type of solar cells is, approximately, 12% [60,65].
In the last place, graphene can be used as material for the counter electrode. This part dictates the
cathodic activity and affects the performance by controlling the restoration of the redox couple. The
values sought are a charge transfer resistance lower than 2–10 Ω·cm
2
. Platinum has been widely used,
but it should be replaced since it has high cost and secondary reactions, although it has the best
performance so far. One of the best possibilities is carbonaceous materials. Lee and his group reported
a 3D nano-foam based on graphene grown by CVD. The values obtained for short-circuit current
density and open circuit voltage are 12.1 mA/cm
2
and 0.7 V, respectively. However, the efficiency
achieved was lower than the similar system with Askay et al. nearly achieved the same value of the
reference device [60].
One advantage of graphene is that it catalyses other redox couples so the low redox potential of the
iodine-based couple can be overcome. For other redox mediators, Pt is no longer the best counter
electrode; graphene nanoplatelets can have a better performance. On the other hand, the inactive basal
plane of graphene limits its interaction with the electrolyte and the reactions rake place in the edges.
As a consequence, some groups have tried to modify the carbonaceous material with polymers or by
doping it with F. A similar efficiency, as with a platinum counter electrode, has been achieved with a
polymer modified graphene. These additions of other components also lead to introduce Pt to increase
the catalytic activity of graphene. The result achieved was a 7.66% in comparison to the 8.16%
obtained for a Pt sputtered electrode [60].
6. Graphene and Graphene Oxide TiO
2
Photocatalysers
The aforementioned photoelectrochemical properties of graphene, rGO and graphene oxide can be
used to develop enhanced photovoltaic systems. The need of renewable sources of energy and the
growing interest in both photodetectors and graphene composites have lead to produce novel materials
to be incorporated and improve existing applications, such as solar cells, organic pollutant
decompositors; H
2
obtaining or CO
2
reduction [60].
Therefore, after the production of graphene, semiconductors and quantum dot graphene-based
composites have been developed, becoming key materials in the functioning and enhancement of those
systems. There is a large number of them, for example, quantum dots such as CdS, CdSe, PbS, ZnS, or
semiconductors, Co
3
O
4
, Fe
2
O
3
, PbS, TiO
2
, WO
3
, ZnO, ZnS, etc., on G/rGO/GO [66–73]. They all have
different properties and therefore, are convenient for different situations. However, TiO
2
has been
widely studied and proved as one of the most interesting photocatalysers since the work of Honda and
Fujishima [74]. Its band gap has sufficient energy to catalyse a large number of chemical reactions. It
is stable and has a great performance [75], low price and good performance. Moreover, it is chemically
Nanomaterials 2013, 3 334


inert and nontoxic [60]. Thus, in this review we will mainly consider the photoelectrochemical properties
of graphene and graphene oxide throughout the enhancement achieved through TiO
2
performance as a
photocatalyser in several different systems.
There are four main preparation methods to for G/rGO/GO-TiO
2
compounds. The first and most
important is hydrothermal/solvothermal methods. There are many variants of that method but, in
general, precursors (GO or rGO, dispersed by means of sonication in an organic solvent, for example
benzyl alcohol, or water and a titanium organometallic compound) are loaded into an autoclave and
react at high pressure and temperature during several hours. Depending on the growth conditions,
rod-shaped TiO
2
[76], nitrogen-doped graphene with TiO
2
[77], nanoparticles [78] and other variants
can be produced.
Solution mixing is started with an ultrasonic mixing and then UV-assisted photocatalytic reduction of
GO [79]. Layer-by-layer rGO-TiO
2
can be produced by spin-coating graphene oxide and TiO
2
and
posterior UV radiation to reduce GO and attach TiO
2
[80]. Another production method is Sol-gel
preparation, where a titanium precursor is injected through syringe pumps into an oleylamine solution
where GO is dispersed. The mixture is then treated thermally to induce the sol-gel reaction [81]. Finally,
in-situ growth the salt is mixed with GO and converted to the oxide while GO is reduced [82].
GO/TiO
2
can be formed in the last three methods by not proceeding with the reduction of GO
to graphene. Besides, also different morphological structures can be produced with GO, such as
TiO
2
nanoparticles wrapped in graphene oxide [83]. In both GO and rGO, TiO
2
can be self-assembled
under several conditions, such as in water/toluene interfaces or anionic sulphate surfactants [84].
Self-assembly techniques are based on hydrophobic/hydrophilic interactions and it is a useful
method to control the growth of the semiconductor on reduced graphene oxide and graphene
oxide’s surfaces [85]. It is remarkable that all the main production methods are based on rGO and not
pristine graphene.
There are two main limitations concerning the use of TiO
2
as a photocatalyser. It has an
electron-hole recombination time of 10
−9
s, with a chemical reaction response of only 10
−8
–10
−3
s; and
it requires UV radiation since it has a too wide band gap (3.2 eV for anatase TiO
2
and 3.0 eV for rutile
phase). Therefore, G/TiO
2
, GO/TiO
2
and rGO/TiO
2
composites should be designed to have visible-light
catalytic activity [10,82].
There are three many reasons that make of graphene and derivatives an excellent material to
combine with TiO
2
. They provide a way to enhance the separation between the electron and the hole
that are produced in a photoexcitation thanks to very high electron mobility. They also enlarge the
absorption range, including the visible region, in which the semiconductor operates by narrowing the
band gap of the semiconductor to 2.8 eV with Ti-O-C bonds and nano-sized Schottky interfaces and
acting as a sensitizer (it directly captures visible light). Finally, they also increase the interaction area
and adsorption of pollutants and dyes with the photocatalyser by creating a π-π interaction with the
delocalized electrons of graphene-based compounds [10,60].
Regarding the mechanism of electron transfer, the TiO
2
particles have affinity for epoxy and
carboxylate groups, where charge transfer is produced by the reduction of those compounds [79].
Oxide groups are required and, as a consequence, pristine graphene would not be suitable in this case.
It has been demonstrated that electrons flow from higher to lower Fermi levels. Since the work
function of graphene is higher—4.42 eV compared to the conduction band of at –4.21 eV with a band
Nanomaterials 2013, 3 335


gap of 3.2 eV—graphene could be used as an electron shuttle so electrons will flow from graphene to
TiO
2
in the contact between those compounds in a process known as percolation mechanism [10,76].
Since graphene is not usually the compound that interacts with TiO
2
but GO/rGO, this may be,
experimentally, the mechanism followed by GO/rGO-TiO
2
composites.
The reaction mechanism is shown in the following [4,10]:
Ti0
2
+hv → Ti0
2
(e
-
+h
+
)
C
2
H
S
OH
======Ti0
2
(e
-
) +C
2
B
4
0B
.
+B
+

(1)
Ti0
2
(e
-
) +u0 → Ti0
2
+iu0 (2)
Ti0
2
(e
-
) +iu0 → Ti0
2
+iu0(e
-
); iu0(e
-
) +0
2
→ 0
2
.-
+iu0 (3)
Ti0
2
(e
-
) +0
2
→ 0
2
.-
+Ti0
2
(4)
These electrons are mostly delocalized. Both electrons and holes react with O
2
and water to form
superoxide and hydroxyl radicals, respectively [4]. Thus, the electrons generated can be used to
generate photocurrent or produce those radicals that will ultimately react with other compounds,
depending on the final aim of the system. In this mechanism, it is shown how semiconductors can take
advantage of the good conductivity, adsorption, transparency and chemical properties of reduced
graphene oxide.
Not only enhancing the electron-hole pair production is important but also to design ways to
produce a more efficient G/rGO/GO-TiO
2
photocatalyst. In order to do that, Zhang et al. studied how
to decrease defects and improve interfacial contact between the carbon-based materials and TiO
2
. GO
is usually prepared with Hummer’s method, which produces a large number of defects on GO surface.
This means that alternative methods to produce this material should be used. The technique used by the
group was solvent exfoliation (SEG). SEG/TiO
2
has, indeed, better properties than GO/TiO
2
obtained
with Hummer’s method by reducing the number of defects but also the number of oxygen groups [86].
Lightcap et al. anchored Ag and TiO
2
to rGO to produce reduction of silver ions into silver
nanoparticles. rGO shows excellent properties to store and shuttle electron. Besides, they established
that, given the conduction band of Titania at –0.5 V vs. NHE and the Fermi level of rGO at 0 V vs.
NHE, the electron transfer is quick and efficient [87].
Although it seems that rGO/TiO
2
and GO/TiO
2
have a promising future in photocatalysis, it still
needs more evidence to prove the superior properties of this composite in comparison to, for example,
other carbon-based materials combined with TiO
2
and other semiconductors [86]. However, many
efforts for developing enhanced applications with this composite are being made and interesting results
have been achieved.
7. Applications
The composite TiO
2
with graphene and its derivatives has large number of applications. We can
divide them into three main groups: Quantum dot sensitized and dye sensitized solar cells; degradation
of organic, ionic and biologic pollutants and water splitting to produce H
2
[86].

Nanomaterials 2013, 3 336


7.1. Water Splitting to Produce H
2

An efficient way to produce photocatalytic hydrogen from water could be vital in the development
of future energy sources. The main problem concerns the fast recombination rate produced in the
photocatalyst excitation. Since the semiconductor produces a charge transfer to graphene or graphene
oxide, it promotes oxygen and hydrogen splitting. Besides, the increase in the absorption range is again
a key contribution of G/rGO/GO in the enhancement of the photocatalytic process. rGO/TiO
2
was
proved to have better hydrogen production than TiO
2
-P25 nanoparticles [88]. Then, a hybrid between
them, TiO
2
-P25-rGO, was produced. This material showed a synergetic effect between the different
components [71,89].
There are two main reasons attributed to the enhancement of the performance. The first is the close
interaction in face-to-face orientation of TiO
2
and rGO. The second is that the potential rGO/rGO

in
comparison to a standard hydrogen electrode (E°(H
+
/H
2
) = 0 V), turns to be −0.08 V; which is less
negative than the conduction band of anatase TiO
2
, ≈ −0.24 V. This promotes the flow of electrons
from TiO
2
towards the rGO sheet and reduce a proton producing hydrogen gas [4,90]. However,
hydrogen evolution rate is still lower than the state-of-the-art photocatalysts such as lanthanum-doped
NaTaO
3
[82].
Finally, Gao et al. conducted an experiment of controlled addition of O
2
into the atmosphere for
controlled production of superoxide radicals. Those molecules can re-oxidize the planar surface of
rGO produced by rGO/TiO
2
and that small quantity of oxygen promotes the hydrogen evolution.
Therefore, the utilization of totally reduced graphene oxide is, in this case, unfavourable and the use of
partially reduced GO is beneficial [91].
Many composites, besides TiO
2
with graphene or any of its derivatives have been developed for
water splitting, such as Zn
x
Cd
1−x
S/rGO, CdS/rGO or WO
3
/rGO. For instance, Jingdong et al. designed
a WO
3
/rGO photoanode to split water. WO
3
has stronger absorption and a longer hole diffusion length.
The potential of the semiconductor CB is more positive than the H
+
/H
2
pair. The electrode generates
2.4 times higher quantity of hydrogen and oxygen than WO
3
on its own and 2.5 higher photocurrent
density. The overall photoreaction is limited by the charge separation and it is only effective at a larger
bias than 0.7 V vs. Ag/AgCl. In darkness the work function rGO is much lower than that for WO
3
and,
as a consequence, the electrons in the CB cannot be injected. Only through interface states the transfer
is possible. However, under illumination, the Fermi energy level in the semiconductor material rises
and the electrons can be transferred directly into rGO. The recombination is then avoided and the
electrons are quickly transported through an external circuit [92].
7.2. Electro-Catalysis: Degradation of Pollutants
One of the most important uses of graphene, rGO and GO/TiO
2
composites is the photodegradation
of ionic, organic and biologic pollutants. Kemp et al. reviewed the applications of graphene
composites for water remediation, where rGO-based Titania compound turned out to be highly
useful [93]. Regarding ionic pollutants, rGO/TiO
2
was proved to have 3.46 times more efficiency in
photocatalysis under visible light than commercial P25-TiO
2
materials. This is produced by the higher
conductivity of rGO and the uniform distribution of nanoparticles achieved by the self-assembly
Nanomaterials 2013, 3 337


technique used [93,94]. The study of rGO/TiO
2
composite modified with P25 and produced by
hydrothermal reaction was also studied by Zhang et al. Figure 2 shows that rGO-based photocatalysis
results in greater and more selective absorption of the dye, in this case methylene blue. The
photocatalytic degradation of malachite green (MB) increases from 20% to 85% with rGO, under a
60-min exposure to UV light. This is 20% greater efficiency than an equivalent composite with CNTs.
It also proportions extended light absorption range, due to the narrowing of the band gap and increased
efficiency in charge separation and transportation; all three mentioned enhancements induced by
reduced graphene oxide [95]. Besides, the reduction of Cr(VI) by up to 91% can be achieved with UV
irradiation of rGO/TiO
2
[93]. Thus, the anchoring of Titania nanoparticles on rGO is a potential
candidate for water waste treatment [96].
Figure 2. Photodegradation of malachite green (MB) under (a) UV light; and (b) Visible
light (λ > 400 nm) over (1) P25; (2) P25-CNTs; and (3) P25-GR photocatalysis
respectively. Reprinted with copyright permission from reference [95]. Copyright © 2010,
American Chemical Society.
As far as the eradication of biological pollutants is concerned, E. coli was eliminated with GO/TiO
2

thanks to the properties exhibited by GO, which is biocompatible and antibacterial [93]. After a
two-hour treatment in 85 µg/mL of GO, the activity of E. coli decreased to 13%. This is produced by
the oxygen groups contained in the GO sheet that react with cell membranes creating oxidative
stress [97].
However, the most important type of compound that can be degraded is organic pollutants. There
have been many studies, with different efficiencies, that degrade compounds such as malachite
green [98], methyl orange MO [76,77], Rhodamine B (Rh. B) [78], methylene blue (MB) [80,84] and
Acid Orange 7 (AO7) [99]. The mechanism behind the degradation, depicted in Figure 3, is similar in
all of them. Electrons cannot flow directly from MB to TiO
2
since their energy levels do not match. A
photoexcited electron from MB flows into Titania’s CB via graphene (Path 1), where radical species
are generated. Pollutants are usually aromatic compounds that create π-π stacking with rGO, raising
the concentration of those molecules near the catalytic semiconductor nanocrystals. The production of
oxidants and the reduction of radicals facilitate the reaction when the pollutant is closer. Therefore, the
photodegradation is enhanced by π-π interactions. Moreover, as with previous pollutants, large surface
area, extended light absorption range, high electron mobility and increased efficiency in charge
Nanomaterials 2013, 3 338


separation improve the photocatalytic activity [98]. There is an alternative electron mechanism that
consists in an electron from the VB of TiO
2
flowing to the conduction band of the semiconductor. This
mechanism is possible by the band gap narrowing produced by graphene sheets. Reactive species that
will degrade the pollutant are then produced (Path 2) [10,81].
Figure 3. Proposed mechanism for the photodegradation of methylene blue (MB) by
graphene-wrapped anatase nanoparticles under visible-light irradiation [10,83]. Reprinted
with copyright permission from reference [83]. Copyright © 2012 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim, Germany.

Some of the pollutants studied are dyes, which are degraded by the use of quantum
dot—Titania–G/GO/rGO systems. In these cases, the photoabsorption can be produced by light
excitation in the QD or in Titania. That is what Zhang and his work-team reported in a rGO/TiO
2

composite with PbS QDs. Both PbS and TiO
2
can get excited by different wavelengths, as a
consequence the photocurrent efficiency was increased. The mechanism is analogous to the previous
example [100]. Ghosh et al. worked with CdSe-rGO-TiO
2
particles. CdSe, with a band gap of
1.6–1.8 eV can accept visible light. The electrons generated in CdSe are transferred to the conduction
band of TiO
2
, whose band gap is 3.0 eV. Besides, rGO can also capture electrons, which are
transferred to the CB of the CdSe and, in the same way, to TiO
2
. This is one case in which, by coupling
semiconductor—quantum dots and rGO—better photocatalytic results can be achieved [101]. Bi
2
O
3
is
another example of sensitized quantum dot that decorates (001) TiO
2
facets on rGO. Hou’s group
proposed a photocatalytic mechanism. TiO
2
has a higher reduction potential than H
+
/H
2
and therefore
more active CB edge potential than Bi
2
O
3
. Photoinduced electrons on TiO
2
are transferred to Bi
2
O
3

compound and the holes to Titania [102].
An interesting study was conducted by Lin et al. and other groups that are researching other types
of ternary composites based on rGO-TiO
2
and Fe
3
O
4
. This photocatalyst can degrade many different
organic dyes (RhB, Orange Pure and Acid Blue 92), has enhanced photocatalytic activity, and can be
recollected with a magnet. Besides, photodissolution of Fe
3
O
4
is inhibited, thus, it has a high stability
and can be reused many times. However, its catalytic activity is not as good as pure rGO/TiO
2
and
GO/TiO
2
composites [103].
To conclude, some of the developed systems could be useful in self-cleaning coating. Under UV
irradiation for TiO
2
systems, the photocatalytic oxidation reactions can degrade organic contaminants.
Nanomaterials 2013, 3 339


In order to be valid for that task, photo-induced catalytic properties play a key role, and rGO/TiO
2

would be a perfect candidate for that task [104].
It has been shown that TiO
2
can be very useful in degradation of organic dye pollutants. At the
same time, it can also function as an effective charge collection layer for Solar cells.
7.3. Solar Cells
Solar cells are one of the applications where the inclusion of TiO
2
graphene-based composites can
enhance the overall performance. At the moment, the most common type of these devices are Si based
solar cells; however, alternatives such as dye sensitized solar cells, quantum dot solar cells and organic
polymer solar cells are increasing in popularity. The excellent conductivity of graphene, acceptability
and mobility of electrons, transparency, wide band tenability and flexibility provided by graphene may
improve the state-of-the-art devices [60].
G/TiO
2
, GO/TiO
2
and rGO/TiO
2
can be used in both dye-sensitized solar cells (DSSC) and quantum
dots solar cells (QDSC). Dye-sensitized solar cells could substitute traditional silicon solar cells in the
future, since they have high photon-to-electron efficiency and low cost [105]. Generally, DSSC have a
film of dye-sensitized TiO
2
, a conductive transparent electrode a counter electrode and an electrolyte.
The dyes are photoexcited and produce an injection of an electron to the semiconductor film. The dye
molecules are restored by the electrolyte, which is a redox couple [60].
The conversion rate achieved so far with TiO
2
electrodes with ruthenium-based dyes is approximately
12%. This low rate is caused by electrons trapping and random pathways. The high specific area and
electron mobility of graphene and derivatives may allow longer lifetimes and better conversion rates.
Kim et al. embedded rGO on the top layers of an inverse opal TiO
2
structure. C-Ti bonds enhance
electron transport, and, therefore, electron injection and collection efficiencies. Besides, the light
harvesting efficiency depends on the dye absorption and the optical properties of the electrode film
[60,105].
The incorporation of rGO sheets improved the electron lifetime by increasing the chemical
capacitance and decreasing the resistance. rGO was used as electron acceptor layer that transports the
negative charged particles, which increased the electrical conductivity. The direct contact of the
semiconductor structure with rGO induced a reduction in the recombination loss. The fact that the
embeddement was limited to some external layers, where the electrons have a higher potential for
recombination loss, improved the electron transport. At the moment, a conversion rate of 7.5% is
achieved, a 55% improvement over DSSC with pure TiO
2
[105]. In addition, as it has been said the
workfunction of rGO is 4.42–4.5 eV, which is higher than the conduction band of TiO
2
, making easier
the electron transport [60,105].
Figure 4 represents how graphene can act as an electron transport layer, matching the different
energy levels. The photoexcited electron produced in the dye is transferred to the CB of TiO
2
. That
electron is then transferred to graphene, which acts as a bridge between the semiconductor and the
conductive substrate [105].
Tang et al. has reported rGO/TiO
2
on top of ITO as photoanode for DSSC. The increase of electron
transport manifested in an increase of the short-circuit current density. They achieved a power conversion
five times higher than pure TiO
2
and conductivity with two orders of magnitude improvement [106].
Nanomaterials 2013, 3 340


Regarding quantum-dot (QD) sensitized solar cells, they have the same structure of DSSC but with
inorganic QD (CdS, CdSe, PbS, and ZnS) instead of organic dyes. The advantages of QD in
comparison to organic dyes are the high extinction coefficients, tuneable band gaps, large intrinsic
dipole moment and good stability. Therefore, the enhancements made with G/rGO/GO-TiO
2
have the
same characteristics of DSSCs’ and the main point would be to improve the electron transport between
those QD and the composite. Figure 5 shows this mechanism, similar to DSSCs, used in QDSSCs;
where rGO acts as an electron bridge between the quantum dot and the CB of the metal oxide
photoanode material [60].
Figure 4. The introduced 2D rGO bridges perform as an electron acceptor and transfer the
electrons quickly. Hence, the recombination and back reaction are suppressed. Reprinted
with copyright permission from [107]. Copyright © 2010, American Chemical Society.

Figure 5. Schematic diagrams of the energy levels in the reduced graphene oxide-CdSe
based quantum dot sensitized solar cell [60]. Reprinted with copyright permission from [108].
Copyright © 2011, American Institute of Physics.

For example, a photoanode of TiO
2
with sensitized Quantum Dots of CdS have been improved by
Zhu et al. by introducing reduced graphene oxide in its structure. The improvement shown in
comparison to the pure photoanode without this material is of 56%. In this case, the conduction band
of TiO
2
(–4.2 eV) was better matched with the work function of the conductive transparent electrode
FTO (–4.4 eV) by means of rGO, whose work function is –4.4 eV. This enhanced the overall
conduction. Therefore, the caption of an electron by the quantum dot is coupled with Titania, as shown
in Figure 6. The semiconductor transports the electron to rGO and this to the electrode. Without rGO,
this linear process would not be that direct, since the electrons from Titania could be transported back
Nanomaterials 2013, 3 341


to the QD in a phenomenon known as back-transport. Recombination of the electrons at the Fermi
level of graphene with the holes at the VB of the quantum dot and the redox couple are inhibited by the
introduction of an interlayer of TiO
2
and rGO. However, some electrons are trapped in the surface
states and band gap of TiO
2
and alternative recombination pathways have to be considered (Processes
4 and 5 in Figure 7). Finally, rGO can also absorb energy from visible light, acting as a sensitizer;
although the quantity of rGO has to be controlled to avoid light harvesting competition [109–111].
Figure 6. Degradation of Rh. B as a function of catalysis and irradiation time. Reprinted
with copyright permission from reference [112]. Copyright © 2013, Elsevier.

Figure 7. Schematic representation of photo-generated electron transfer processes in a
layered reduced graphene oxide/quantum dot (QD) structure with TiO
x
interlayer (a) and
the Energy Band Diagram (b) showing the main electronic processes at the interface in
QDs: (1) Electron injection; (2) electron transfer; (3) Trapping of the electron at surface
states; the two charge recombination pathways of trapped electron recombination with;
(4) the hole at the valence band of QDs and; (5) the oxidized redox couple; (6) hole extraction.
The recombination between the electron at Fermi level of rGO and the hole at the valence
band of QDs and the oxidized redox couple was inhibited by TiO
x
layer. Reprinted with
copyright permission from reference [111]. Copyright © 2011, American Chemical Society.

Nanomaterials 2013, 3 342


7.4. Other Applications Based in G/TiO
2
, rGO/TiO
2
and GO/TiO
2
Composites
Moreover, there are some other applications of G/TiO
2
, rGO/TiO
2
and GO/TiO
2
where the
enhancement produced by the carbon-based materials is clear. For example, some developments such
as the reduction of CO
2
[113] and enhancements for lithium-ion batteries (used as an anode in
combination with LiFePO
4
can enhance the cycling performance [114–116]) that will define new
possibilities for this composite.
8. Other Graphene-Based Photocatalytic Composites
It is remarkable that graphene and its derivatives can enhance the photocatalytic properties of
different materials, apart from Titania. Good examples of that are quantum dots such as CdS and ZnS
and other semiconductors such as ZnO combined with graphene, rGO or GO.
CdS is a photocatalyser under visible light that has a band gap of 2.42 eV, although it self-oxidises
liberating Cd
2+
ions and has a fast electron-hole recombination, which limits its photocatalysis activity.
There are several ways to improve the photocatalytic activity of CdS; for example, binding it to other
semiconductors or noble metals. Another way is to bind it with a mesoporous or macroreticular material
creating a composite were the electrons created by the photoexcitation can move freely while the hole
is trapped in the CdS nanoparticles. For that purpose, large surface area and conductive materials are
required [1,117]. This could be achieved by using graphene or derivatives, where the efficient electron
transport from the semiconductor to the carbon-based material would enhance the photoelectronic
response. Nevertheless, studies that combine these two materials are not that common [117].
Zhou et al. used solvothermal/hydrothermal method to produce a graphene-based magnetic
composite by generating CdS and Fe
3
O
4
nanoparticles at the same time [118]. In the production of
QDs, CdS QDs show photoluminescence responses while rGO/CdS QD do not. This indicates an
efficient separation of the electron-hole pair that produces a very strong photovoltaic response [66,68].
Proof of the enhanced catalytic activity is that rGO/CdS exhibits better performance than GO and
CdS on their own in the photodegradation of organic and inorganic compounds, such as Rhodamine B,
as shown in Figure 6. This fact supports the enhancement of the aforementioned electron transfer, which is
used to produce oxygen peroxide radicals O
2

and hydroxyl radicals OH

by the electron and the hole
respectively. Those compounds will ultimately react with Rh. B producing its degradation [112].
It was also used in the degradation of other compounds such as methylene blue, where an efficiency
of 94% degradation was achieved by means of visible light; in comparison to pure CdS, that only
achieved a degradation of 38% [119]. The amount of rGO or GO is a key issue in the optimal
preparation of the photocatalyst [119,120]. Graphene oxide can also be used in degradation activities
with CdS. Synthesized by two phase mixing, it can degrade bacteria (E. coli, and B. subtilis) and
Rh. B, methyl orange to produce hydrogen [121] and Cr
6+
[122].
Another example of graphene’s possibilities would be rGO/ZnS and GO/ZnS composites. ZnS is a
II–VI semiconductor with a wide band gap (3.75 eV) that is of interest since it can be used, for
example, in field effect transistors, LEDs, photocatalysis and solar cells [123,124]. Recently, quantum
dot nanocomposites based on graphene and derivatives have been developed by different production
Nanomaterials 2013, 3 343


methods such as hydrothermal [123,125,126]; solvothermal synthesis [68,69] or microwave-assisted
synthesis [127] amongst others.
The good photocatalytic activity of this compound is a consequence of the rapid photo-excitation,
combined with the highly negative reduction potential of the excited electrons [127]. Hu and his group
proved the photocatalytic activity of the compound by degrading methylene blue (MB) in water. As
expected, rGO raised the electron mobility, acting as an acceptor of negative charge, with good
interfacial transfer results that, ultimately, achieved the non-recombination of the pair electron-hole.
Besides, another property of rGO that enhanced the photocatalytic activity of the semiconductor is the
large surface area, which could disperse the quantum dots so better photon absorption can be achieved
and reduces the size of the quantum dots [125,127].
Pan and Liu assigned the charge transfer mechanism to a chemisorption interaction. The photons
cause a resonant charge transfer between the semiconductor and the adsorbate, forming specific
complexes. Once the electron is excited into the conduction band of ZnS, they interact with reduced
graphene oxide and get energy from the excitation levels of this material. In this case, they are then
recombined with the holes produced in ZnS leading to better photoluminescence results of the
quantum dot. Moreover, if the quantum dots has reduced size, they also have more surface states that
can easily coordinate with rGO [125].
Photocatalysis is also possible under visible light. This is a result of a narrowed band gap to
3.45 eV for 5%rGO/ZnS (although it is still too broad to be photoexcited by visible light) and the
contribution of reduced graphene oxide. rGO is photoexcited by visible light and the electron is then
transferred to the conduction band of the ZnS. Thus, the carbon based material acts as a visible light
photocatalyser in a similar way to organic dyes. This behaviour is different to the previously charge
transfer mechanism, common for G/rGO/GO-semiconductor composites. Graphene and derivatives can
be used, therefore, as photosensitizers [128]. ZnS nanocomposites have been used in many photocatalytic
activities, such as photoreduction of CO
2
,

water splitting or photoreductive dehalogenation [129].
Graphene, rGO and GO composites with this semiconductor have, therefore, an interest future in
photocatalysis, similarly to Titania.
As a final example of the capabilities of graphene, reduced graphene oxide and graphene oxide in
photocatalysis, it is interesting to mention their composites with ZnO. This is a semiconductor with a
3.2 eV band gap that is interesting since it is benign to the environment and has a low recombination
probability, its valence band is only formed with d orbitals while the conduction band is formed by
p-hybridized orbitals [1].
The photocatalytic properties of rGO/ZnO have been proven by many groups through the
degradation of methylene blue under UV light [130–132]. Zhou et al. described the reasons that are
attributed to the enhanced performance of the semiconductor in the degradation of the organic pollutant by
reduced graphene oxide. As in previous cases, the π-π interaction between the semiconductor and the
carbon based material improves the absorbance of MB. The electron ejected from ZnO is accepted by
the rGO layer, which was then used to degrade the pollutant. Moreover, the short distance between
rGO and zinc peroxide enables the fast transfer of the excited electron [130]. This short chemical
bonding reduces rGO/ZnO band gap to 2.90 eV, and therefore, reduced graphene oxide also induces
visible-light absorption by the modified electron-hole production process [131].
Nanomaterials 2013, 3 344


It is interesting the in-depth study of the mechanism of electron transfer that could happen in the
degradation of most pollutants done by Ahmad et al., which is depicted in the Figure 8. The dye is
excited and acts as sensitizer under visible light which then transfers the electron to the conduction
band of ZnO becoming a cationic dye radical, followed by the consequent degradation of the organic
compound. The energy level of reduced graphene oxide, −4.42 eV, is lower than the conduction band
of ZnO, −4.05 eV. Since MB has a workfunction in excited state of −3.60 eV, the direct transfer from
excited MB to ZnO is not possible. However, the reduction in the effective band gap of ZnO by
combining it with rGO allows this transference through the reduced graphene oxide layer. Besides, the
narrowed band gap allow the absorption of visible light by rGO/ZnO, which also contributes to
degrading the pollutant [131]. The enhancement produced by the 2% in weight of graphene in
rGO/ZnO produces up to four times more photocatalytic activity than pure ZnO [133].
Figure 8. Two proposed mechanisms for the photodegradation of MB by rGO/ZnO
composite under visible light and energy diagram of excited MB, graphene and the
conduction band of ZnO. (a) The excitation of the semiconductor produced by light
irradiation generates an electron-hole pair. The reaction with the organic pollutant takes place
in the movement of those charges towards the particle surface. (b) The dye, which act as a light
sensitizer, is excited and transfers electrons. It becomes a cationic radical that self-degrades.
Reprinted with copyright permission from reference [131]. Copyright © 2013, Elsevier.

Since the energy levels of rGO enhance the electron transfer, avoid recombination and allow visible
light absorption (although this may reduce the photocatalytic activity by light harvesting competition);
several photocatalytic activities have been performed to exploit this effect. For example, as well as
other organic pollutants like Rhodamine 6G [134], also metal particles as Cr(VI) have been proved to
Nanomaterials 2013, 3 345


be reduced with UV light by using rGO/ZnO composite [135]; the fabrication of a fast UV photodetector
from rGO/ZnO shell-core structure [136] or the fabrication as electrode materials for supercapacitors
with high capacitance values (59 F/g, 61.7 F/g and 146 F/g) and power density (4.8 kW/kg) [137]
amongst others. Regarding the activity under solar light, three-component composites have also been
developed, like ZnFe
2
O
4
/ZnO immobilized on reduced graphene oxide (ZnFe
2
O
4
has a narrow band
gap of 1.9 eV that allows the solar light caption); which also has magnetic properties that enable an
easier separation, and therefore reuse, of the catalyst [138].
8.1. Graphene-QD Composites as Photodetectors
Quantum dots combined with a graphene derivative seem to have great potential for future
photocatalytic purposes. Within the potential applications, the possibilities provided by their fast
photon detection response should not be forgotten. Graphene-based photodetectors have been limited
to a photoresponse of ≈10
−2
A/W since it has weak light absorption and absence of multiple
photoexcitation. Nevertheless, its fast response time and broad spectral width are of great interest in
photodetection. On the other hand, colloidal quantum dot films have poor carrier mobility and limited
absorption range. Graphene, with an absorption range from UV to terahertz range overcomes the
“long-wavelength limit”. Besides, the maximum operating bandwidth of photodetectors is restricted by
their finite duration of photogenerated current. By creating a composite of monolayer or bilayer
graphene with colloidal quantum dots, a responsivity of ≈10
7
A/W can be achieved by using the high
charge mobility on graphene layers [9,139].
Konstantatos et al. claim that the key of the enhancement in the light absorption of graphene is the
implementation of photoconductive gain, i.e., the ability to generate multiple charge carriers with a
single photon. Thus, they developed a G/PbS composite with ultrahigh photodetection gain (Figure 9),
high quantum efficiency, high sensitivity and gate-tuneable photodetection. The channel of the
phototransistor is a monolayer of graphene decorated with PbS QDs that act as a photon absorbing
material on top of a Si/SiO
2
substrate. The functioning mechanism that they proposed is the following:
The QDs absorb a photon and creates an electron-hole pair. They are separated at G/QD interface
induced by an internal electric field that leads to a band bending, caused by the work function
mismatch between the two components [139]. By using an internal field near the quantum
dot-graphene interfaces (it can also be done with an external field), effective photocurrent responses
can be achieved, with efficiencies up to a 30% of electron-hole separation [9]. The holes are
transferred to the graphene layer and the electrons are trapped in the QD [139]. The zero-gap of
graphene allows the transmission of the positive carriers through the potential barriers [2]. Positive
charges are re-circulated many times, resulting in an overall gain. In summary, the benefits that
monolayer graphene provides are gate-tunable sensibility, speed and spectral selectivity [139]. This
photodetection gain is relevant in different applications, such as optoelectronic circuits, quantum
information technology, biomedical imaging or remote sensing [139].

Nanomaterials 2013, 3 346


Figure 9. Scheme the hybrid G/PbS phototransistor. Reprinted with copyright permission
from reference [139]. Copyright © 2012, Nature Publishing Group.

8.2. Other Applications of Graphene-QD Composites
In addition to photodetector systems, the enhancement in optoelectronic properties induced by
graphene in these composites is useful in different fields and applications. Zhang et al. reviewed the
synthesis, assembly, functionalization and applications of graphene-QD composites and highlighted
photovoltaic devices, supercapacitors, organic light-emission diodes, fuel cells as a substitute of Pt
catalysts for the oxygen reduction reaction and biosensing and bioimaging as other fields where those
composites can offer future solutions [140].
9. Conclusions
Graphene-quantum dot systems can work as ultrafast photodetector with spectral selectivity. Such
an application has a very strict quality requirement on graphene and it is generally using
defect-free/less defect monolayer graphene from CVD method. Reduced graphene oxide (rGO) and
graphene oxide (GO) have shown great possibilities in composite generation. They can be combined with
semiconductors and quantum dots to generate bi and tri-component composites. The wide range of
superlative properties of graphene derivatives benefits the photoelectrochemical performance of many
materials in multiple aspects. For example, the big surface area with delocalized bonds, in a similar
way as “giant” aromatic compound, allows the π-π stacking of several components, which leads to
intimate interactions between substrate and organic compounds such as pollutants.
Moreover, the interactions between the oxide groups of GO or rGO and the semiconductor also lead
to a close interaction between these two components. This close distance between them enhances the
conductivity of photoexcited electrons and reduces the recombination rate of the electron-hole pair.
Besides, the high electron mobility of the electron in a layer of graphene also contributes to that effect.
This can be useful, for instance, as a bridge between the semiconductor and an organic compound to
enhance its degradation.
Nanomaterials 2013, 3 347


Many of the most important semiconductor catalysers have a wide band gap that is mainly excited
by UV light. rGO narrows the effective band gap of the semiconductor material. It has a wide spectrum
of light absorption, thus, it can also act as a sensitizer to capture visible light. However, this mechanism
can either lead to enhance the photocatalytic activity or act as a competitor in light harvesting. This
would reduce the performance of the semiconductor. A precise control of the parameters and an
in-depth study of the reaction mechanisms are required. It seems feasible to introduce rGO and GO
in next-generation photocatalytic structures since, a priori; those components lead to enhanced
performance results. Although more research is required to fully understand and exploit graphene and
derivatives possibilities, current investigation indicates that the performance achieved so far without
these materials can be surpassed, and many combinations of different semiconductors, carbon structures,
and graphene and its derivatives would be required to take full advantage of this material. By creating
new, more complex composites, with tuned coordinated energy band gaps between the different
components, we would be able to achieve a high performance photocatalytic response.
However, it is remarkable that, in most cases, it is rGO and not pristine graphene that is used in the
development of composites. This is a direct consequence of the different chemical properties of
graphene and graphene oxide. The latter allows tailoring and functionalization of the layer, which is
much more difficult in monolayer graphene. Nevertheless, it would also be interesting to control the
position and concentration of oxygen groups to enhance the optoelectronic properties of graphene,
which are more convenient and are affected by the oxygenation of the surface. For that reason, they
should be treated as independent compounds and alternative production methods that reduce the number of
defects, with intermediate properties, such as electrochemical exfoliation, should be developed.
In conclusion, GO and rGO can be mixed with quantum dots and many other different semiconductors
as composites while, on the other hand, pristine monolayer graphene is usually combined with fine-tuned
quantum dots to enable a decent photodetector, which uses intrinsic physical properties from
defect-free/less defect graphene. Different photoelectrochemical applications will have different
requirements on properties and material costs, which is also determined from their different scalability
of manufacturing. Graphene and its derivatives obviously provide us various options to explore and it
will be exciting to witness how this new type of material will revolutionize/improve the materials used
in our daily life.
Conflict of Interest
The authors declare no conflict of interest.
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